Process for preparing fluorine-containing halogenated hydrocarbon compound

ABSTRACT

The present invention provides a process for preparing a fluorine-containing halogenated hydrocarbon compound by fluorinating, in a reaction field where an antimony halide compound represented by the general formula: 
     
       
         SbCl p F 5−p   (I) 
       
     
     wherein p is a value within a range from 0 to 2, and hydrogen fluoride and a halogenated hydrocarbon compound as a raw material exist, the halogenated hydrocarbon compound in a molar ratio of the antimony halide compound to hydrogen fluoride within a range from 40/60 to 90/10. According to this process, a fluorine-containing halogenated hydrocarbon compound (HFC), which is important as a substitute compound of CFC or HCFC, can be prepared economically advantageously with good selectivity while suppressing a corrosive action of a reaction vessel.

This application is the national phase under 35 U.S.C. § 371 of PCTInternational Application No. PCT/JP00/08141 which has an Internationalfiling date of Nov. 20, 2000, which designated the United States ofAmerica.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention generally relates to a process for preparing afluorine-containing hydrocarbon compound such as hydrofluorocarbons(HFC).

2. Description of the Related Art

Fluorine-containing hydrocarbon compounds such as hydrofluorocarbons(HFC) are used as substitute compounds of chlorofluorocarbons (CFC) andhydrochlorofluorocarbons (HCFC) which having a strong action ofdepleting an ozone layer, and are important compounds used as blowingagents, coolants, cleaners or propellant which do not deplete ozone inthe current industry.

It has already been known to use an antimony compound as a catalyst inthe process for preparing a hydrofluorocarbon. For example, JapanesePatent Kokai Publication No. 169829/1991 discloses a process forpreparing CF₃CHCl₂, CF₃CHCIF or CF₃CHF₂ by fluorinating CClF₂CHCl₂without directly using hydrogen fluoride. Japanese Patent KokokuPublication No. 91202/1995 discloses a process for preparing CF₃CHCl₂ byfluorinating CClF₂CHCl₂ or CCl₂FCHCl₂, and WO96/01797 discloses aprocess for preparing 1,1,1,3,3-pentafluoropropane by fluorinating1,1,1,3,3-pentachloropropane with hydrogen fluoride in the presence ofan antimony halide compound.

Although it is known that the antimony halide compound is a highlycorrosive compound, none of the patent publications mentioned aboverefers to corrosion of a reaction apparatus or prevention of suchcorrosion of a reaction apparatus. According to the description ofexamples of these publications, the concentration of the antimony halidecompound used as a catalyst is usually within a range from about 0.1 to10 mol based on 100 mol of hydrogen fluoride, and is within a range fromabout 20 to 30 mol at most. However, the inventors of the presentinvention confirmed that, when using the antimony halide compound havinga concentration within such a range as the catalyst, it exhibits ametallic corrosion action in a very high level.

As described in Japanese Patent Kokai Publication No. 169829/1991, whenthe fluorination is conducted only by using a fluorine atom-containingantimony halide compound in the absence of hydrogen fluoride in thesystem, an operation of refluorinating the consumed antimony halidecompound and an apparatus therefor are required. Therefore, the processcan not be said to be economically advantageous.

WO98/33754 discloses a process for fluorinating1,1,1,3,3,3-hexachloropropane in a solvent of1-chloro-1,1,3,3,3-pentachloropropane or 1,1,1,3,3,3-hexafluoropropaneand Japanese Patent Kokai Publication No. 217704/1996 discloses aprocess for simultaneously fluorinating dichloromethane and1,1,1-trichloroethane, respectively, and these publications describethat the objective compound can be obtained in a good yield and that thecorrosion prevention effect of the reaction apparatus is also achieved.

However, as described in WO98/33754, the process using the product orthe intermediate product as the solvent is not deemed to be economicallyadvantageous because the volume of a reaction vessel should be increasedcorresponding to the increase of the amount of the solvent to be used.Furthermore, since some compound has poor compatibility with hydrogenfluoride, phase separation between the hydrogen fluoride and the solventis likely to occur in the reaction vessel, thereby to drastically lowerthe reaction efficiency. Therefore, such a process is applicable tolimited cases.

The process of simultaneously fluorinating dichloromethane and1,1,1-trichloroethane described in Japanese Patent Kokai Publication No.217704/1996 is economically disadvantageous because when any one productis required, the other product which is not necessary is prepared.

In WO98/33754 and Japanese Patent Kokai Publication No. 217704/1996,although the amount of the antimony halide compound based on hydrogenfluoride is not specifically prescribed, the amount is several mol % atmost as described in examples of the former publication and there is notan example wherein the antimony halide compound is used in a highconcentration. On the other hand, the latter publication describes that,since the temperature of the reaction vessel is maintained at atemperature higher than a boiling point of hydrogen fluoride under areaction pressure, hydrogen fluoride does not exist in a liquid state inthe reaction vessel. That is, this description shows that theconcentration of the antimony halide compound is nearly 100 mol % basedon hydrogen fluoride. The absence of hydrogen fluoride in the reactionsolution is not suited to efficiently conduct the reaction because thefeed of a fluorine source in the fluorination reaction is delayed.

As the corrosion-proof fluorination process, Japanese Patent KokaiPublication No. 233102/1995 discloses a process using a reaction vesselmade of a fluororesin and Japanese Patent Kokoku Publication No.88591/1995 discloses a process for lowering the corrosiveness bymaintaining a water content in a raw material at a low level,respectively. However, it is not possible to provide an equipmentcomprising a resin-lined instrument with a heating equipment in theprocess using the reaction vessel made of the fluororesin described inJapanese Patent Kokai Publication No. 233102/1995 as described in thespecification thereof, so that it is difficult to control the reactiontemperature. In addition, the raw material is fed in a gaseous form and,therefore, a pre-heater of the raw material is required, resulting inhigh equipment cost. The process for maintaining the water content inthe raw material at a low level described in Japanese Patent KokokuPublication No. 88591/1995 is not deemed to be economical becausedehydration of an organic material requires addition of a dehydratingagent and distillation and also dehydration of hydrogen fluoriderequires electrolysis and addition of a fluorine gas, resulting inincrease of the number of the steps.

It has hitherto been known that a hydrogen fluoride solution ofSbCl_(p)F_(5−p) has very high corrosiveness and the reactivity of thehydrogen fluoride solution of SbCl_(p)F_(5−p) with respect to thereaction of fluorinating the organic material increases with theincrease in concentration thereof. The commonly used concentration waswithin a range from 1 to 10 mol %, as disclosed in examples ofWO96/01797, in view of the economical efficiency.

However, the present inventors found that, when using SbCl_(p)F_(5−p) ina concentration, which is comparatively higher than that has hithertobeen used, the corrosiveness of SbCl_(p)F_(5−p) is lowered within aconventionally used concentration range by the same degree as in thecase of a comparatively low concentration range, or a concentrationlower than a lower limit in the conventionally used range. Consequently,the present invention has been completed.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a process for preparinga fluorine-containing halogenated hydrocarbon compound (HFC), which isimportant as a substitute or an alternative compound of CFC or HCFC,economically advantageously with good selectivity while suppressing acorrosive action of a reaction vessel.

The inventors have intensively studied to achieve the object describedabove and devised the present invention which provides a process capableof suppressing the corrosion of a reaction vessel made of a metal whilemaintaining a high fluorinating ability of an antimony halide compoundby using a mixture of hydrogen fluoride and an antimony halide compound,which mixture contains the antimony halide compound in a comparativelyhigh concentration. The above mixture of the antimony halide compoundand hydrogen fluoride may also be expressed that it exists in the formof a hydrogen fluoride solution containing an antimony halide compoundin a high concentration at normal temperature under normal pressure.

In an aspect, the process for preparing a fluorine-containinghalogenated hydrocarbon compound of the present invention ischaracterized by fluorinating, in a reaction field where an antimonyhalide compound represented by the general formula:

SbCl_(p)F_(5−p)  (I)

wherein p is a value within a range from 0 to 2, and hydrogen fluorideand a halogenated hydrocarbon compound as a raw material exist, thehalogenated hydrocarbon compound in a molar ratio of the antimony halidecompound to hydrogen fluoride within a range from 40/60 to 90/10,thereby to prepare a fluorine-containing halogenated hydrocarboncompound.

Particularly, the fluorine-containing halogenated hydrocarbon compoundcan be prepared by bringing a mixture containing 40 to 90 mol % of theantimony halide compound and 60 to 10 mol % of hydrogen fluoride intocontact with the halogenated hydrocarbon compound.

It can be considered that the antimony halide compound functions as aso-called catalyst in this process. According to the process of thepresent invention, there can be prepared a fluorine-containinghalogenated hydrocarbon compound wherein one or more halogen atoms otherthan fluorine atoms in the halogenated hydrocarbon compound used as araw material are substituted with fluorine atoms. In this case,substitutable halogen atoms are, for example, one or more halogen atomsselected from chlorine atom, bromine atom and iodine atom.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

In the present invention, as the antimony halide compound represented bythe general formula: SbCl_(p)F_(5−p), a single compound can be used, asa matter of course, and there can also be used a mixture (or acomposition) of two or more kinds of compounds having the compositionrepresented by the above general formula. Therefore, in the case of thesingle compound, the value of p is an integer of 0, 1 or 2. When usingthe composition of two or more kinds of compounds, the value of p iswithin a range from 0 to 2.

The reason why the value of p was defined as described above in thepresent invention is based on the following fact that was found out.That is, regarding the antimony halide compound wherein the value of pis not within a range form 0 to 2, the reactivity (conversion ratio,selectivity) with respect to the above fluorination reaction isdrastically lower than that of the antimony halide compound wherein thevalue of p is within a range from 0 to 2.

When using the antimony halide compound wherein the value of p is 3 ormore, since such compound has poor reactivity, it becomes necessary toraise the reaction temperature to make up for poor reactivity. However,when the reaction temperature is raised, the reaction of chlorinating anorganic material is liable to occur. As a result, antimony atoms of thiscompound are converted from Sb (V) to Sb (III) in a reduced valencestate. Therefore, the reactivity of the fluorination reaction due to theantimony halide compound is further lowered against the intentiondescribed above. Therefore, it can be said that the value of p within arange from 0 to 2 is an essential constituent in the compoundSbCl_(p)F_(5−p) when using it as the catalyst of the fluorinationreaction in the present invention.

Specifically, the antimony halide compound (SbCl_(p)F_(5−p)), which canbe used in the present invention, includes at least one compoundselected from the group consisting of SbF₅, SbClF₄ and SbCl₂F₃. When anycompound among this group is used alone, the value of p is an integer of0, 1 or 2. There can also be used, as the antimony halide compound inthe present invention, a mixture (composition) which is obtained bymixing SbCl₅ with SbF₅ in a predetermined ratio and has a compositionrepresented by the general formula: SbCl_(p)F_(5−p). For example, acomposition represented by the general formula: SbCl_(p)F_(5−p) can beprepared by mixing 0.8 mol of SbF₅ with 0.2 mol of SbCl₅ and thiscomposition can be used as the antimony halide compound in the presentinvention. There can also be used, as the antimony halide compound inthe present invention, a composition which is prepared by mixing 100 to60 mol % of SbF₅ with SbCl₅ as the balance and is represented by theformula:

SbCl_(p)F_(5−p)

wherein 0≦p≦2. The antimony halide compound in the present invention canalso be prepared by an already-known process of reacting SbF₅ with HCl,or reacting SbCl₅ with HF in a predetermined ratio, or reacting SbF₃with Cl₂.

The content of SbCl_(p)F_(5−p) in the mixture of the antimony halidecompound (SbCl_(p)F_(5−p)) and hydrogen fluoride (the concentration ofSbCl_(p)F_(5−p) in a hydrogen fluoride solution of SbCl_(p)F_(5−p) whenconsidered as the hydrogen fluoride solution of SbCl_(p)F_(5−p)) ispreferably within a range from 40 to 90 mol %, and is more preferablyfrom 50 to 80 mol %.

The reason why the content of SbCl_(p)F_(5−p) was defined as describedabove is based on the following results found out by examining thecorrosiveness of SbCl F_(5−p) as a function of the concentration ofSbCl_(p)F_(5−p) in the hydrogen fluoride solution of SbCl_(p)F_(5−p).That is, when the concentration is within a range from 0 to 0.5 mol %,the corrosiveness is in a low level. When the concentration is within arange from 0.5 to 5 mol %, the corrosiveness is enhanced with theincrease of the concentration. When concentration is within a range from5 to 10 mol %, the corrosiveness exhibits a very high level and reachesmaximum. When the concentration exceeds 10 mol % and further increases,the corrosiveness makes a sudden change and tends to be lowered. Whenthe concentration is within a range from 10 to 40 mol %, thecorrosiveness is in a comparatively high level but is gradually lowered.When the concentration is 40 mol % or more, the corrosiveness is loweredto a low level by the same degree as in the case of the concentrationwithin a range from 0 to 0.5 mol %.

As described above, although the corrosiveness is comparatively low evenwhen the concentration of SbCl_(p)F_(5−p) is 0.5 mol % or less, it cannot be said to be practical with respect to the fluorination reactionbecause of low concentration.

When the concentration of SbCl_(p)F_(5−p) in the hydrogen fluoride ofSbCl_(p)F_(5−p) is lower than 40 mol %, the corrosiveness is rapidlyenhanced. Therefore, it is not preferred. On the other hand, when theconcentration is higher than 90 mol %, the reaction rate is lowered bythe reduction of the fluorine content of the catalyst. Therefore, it isnot preferred with respect to the fluorination reaction.

The reaction temperature in the fluorinating reaction of the halogenatedhydrocarbon compound in the present invention is preferably within arange from −10 to 150° C., and more preferably from 0 to 120° C. Thepressure of the reaction system is preferably within a range from 0.01to 5 MPa, and more preferably from 0.1 to 1.2 MP.

In the process of the present invention, the hydrocarbon compound usedas a raw material can be represented by the general formula:

C_(n)H_(x)Cl_(y)F_(z)  (II)

wherein n is any integer of from 1 to 3,

when n is 1, x is any integer of from 0 to 2, y is any integer of from 1to 4, z is any integer of from 0 to 2, and x, y and z satisfy therelationship: x+y+z=4,

when n is 2, x is any integer of from 0 to 3, y is any integer of from 1to 6, z is any integer of from 0 to 3, and x, y and z satisfy therelationship: x+y+z=4 or x+y+z=6, and

when n is 3, x is any integer of from 0 to 3, y is any integer of from 1to 8, z is any integer of from 0 to 6, and x, y and z satisfy therelationship: x+y+z=6 or x+y+z=8.

When the halogenated hydrocarbon described above is applied to theprocess of the present invention, there can be obtained a halogenatedhydrocarbon compound wherein the number of fluorine atoms in a moleculewas increased by the fluorination reaction. The product obtained by theprocess of the present invention can be represented by the generalformula:

C_(n)H_(x)Cl_(y-a)F_(z+a)  (III)

wherein n is any integer of from 1 to 3,

when n is 1, x is any integer of from 0 to 2, y is any integer of from 1to 4, z is any integer of from 0 to 3, a is any integer of from 1 to 4,and x, y, z and a satisfy the relationships: x+y+z=4 and y≧a,

when n is 2, x is any integer of from 0 to 3, y is any integer of from 1to 6, z is any integer of from 0 to 4, a is any integer of from 1 to 6,and x, y, z and a satisfy the relationship: x+y+z=4 or x+y+z=6 and therelationship: y≧a, and

when n is 3, x is any integer of from 0 to 3, y is any integer of from 1to 8, z is any integer of from 0 to 7, a is any integer of from 1 to 8,and x, y, z and a satisfy the relationship: x+y+z=6 or x+y+z=8 and therelationship: y≧a.

Specifically, when using, as the raw material, at least one halogenatedhydrocarbon compound selected from the group consisting of CH₂Cl₂ andCH₂ClF, at least one fluorine-containing halogenated hydrocarboncompound selected from the group consisting of CH₂ClF and CH₂F₂ can beprepared.

When using, as the raw material, one or more halogenated hydrocarboncompounds selected from the group of compounds represented by themolecular formulas: C₂Cl₄, C₂HCl₃, C₂HCl₅, C₂HCl₄F, C₂HCl₃F₂, C₂HCl₂F₃,C₂HClF₄, C₂H₂Cl₄, C₂H₂Cl₃F, C₂H₂Cl₂F₂ and C₂H₂ClF₃, one or morefluorine-containing halogenated hydrocarbon compounds represented by themolecular formulas: C₂HCl₄F, C₂HCl₃F₂, C₂HCl₂F₃, C₂HClF₄, C₂HF₅,C₂H₂Cl₃F, C₂H₂Cl₂F₂, C₂H₂ClF₃ and C₂H₂F₄.

The compound as the raw material represented by the above molecularformula includes, for example, CCl₂═CCl₂, CHCl₂CCl₂F, CHCl₂CClF₂,CHCl₂CF₃, CHClFCF₃, CHClFCCl₂F, CHClFCClF₂, CHF₂CCl₂F, CHF₂CClF₂,CHCl═CCl₂, CH₂ClCCl₂F, CH₂ClCClF₂, CH₂ClCF₃, CH₂FCCl₂F and CH₂FCClF₂,and the fluorine-containing halogenated hydrocarbon compound as theproduct represented by the above molecular formula includes CHCl₂CCl₂F,CHCl₂CClF₂, CHCl₂CF₃, CHClFCF₃, CHClFCCl₂F, CHClFCClF₂, CHF₂CCl₂F,CHF₂CClF₂, CHF₂CF₃, CH₂ClCCl₂F, CH₂ClCClF₂, CH₂ClCF₃, CH₂FCF₃,CH₂FCCl₂F, CH₂FCClF₂ and CH₂FCF₃.

When using, as the raw material, at least one compound selected from thegroup consisting of CCl₃CH₂CHCl₂, CCl₂FCH₂CHCl₂, CClF₂CH₂CHCl₂,CF₃CH₂CHCl₂, CF₃CH₂CHClF, CCl₃CH₂CHClF, CCl₂FCH₂CHClF, CClF₂CH₂CHClF,CCl₃CH₂CHF₂, CCl₂FCH₂CHF₂, CClF₂CH₂CHF₂, CHCl₂CH═CCl₂, CHCl₂CH═CClF,CHCl₂CH═CF₂, CHClFCH═CCl₂, CHClFCH═CClF, CHClFCH═CF₂, CHF₂CH═CCl₂,CHF₂CH═CClF, CCl₃CH═CHCl, CCl₂FCH═CHCl, CClF₂CH═CHCl, CF₃CH═CHCl,CCl₃CH═CHF, CCl₂FCH═CHF and CClF₂CH═CHF, at least onefluorine-containing halogenated hydrocarbon compound selected from thegroup consisting of CCl₂FCH₂CHCl₂, CClF₂CH₂CHCl₂, CF₃CH₂CHCl₂,CF₃CH₂CHClF, CCl₃CH₂CHClF, CCl₂FCH₂CHClF, CClF₂CH₂CHClF, CCl₃CH₂CHF₂,CCl₂FCH₂CHF₂, CClF₂CH₂CHF₂, CHCl₂CH═CClF, CHCl₂CH═CF₂, CHClFCH═CCl₂,CHClFCH═CClF, CHClFCH═CF₂, CHF₂C H═CCl₂, CHF₂CH═CClF, CCl₂FCH═CHCl,CClF₂CH═CHCl, CF₃CH═CHCl, CCl₃CH═CHF, CCl₂FCH═CHF, CClF₂CH═CHF,CF₃CH₂CHF₂, CF₃CH═CHF and CHF₂CH═CF₂

The examples described above do not limit the halogenated hydrocarboncompound, which can be applied to the process of the present invention,and any hydrocarbon compound which satisfies the conditions representedby the general formula: C_(n)H_(x)Cl_(y)F_(z) can be applied to theprocess of the present invention. As a result, a fluorine-containinghalogenated hydrocarbon compound represented by the general formula:C_(n)H_(x)Cl_(y)F_(z) a can be obtained.

In the process of the present invention, the relationship between theantimony halide compound and the raw material, which are introduced intoa reaction field and are brought into contact with each other, is asfollows. In the case of the batch-wise reaction, it is advantageous toset the feed amount of the halogenated hydrocarbon compound to besubstituted so that the applicable amount of F (fluorine atom) beinglarger than the amount of Cl (chlorine atom) of such halogenatedhydrocarbon compound to be substituted. For example, since the amount ofF which can be utilized from the system using 8 mol of SbF₅ and 2 mol ofHF is 18 mol (=16 mol+2 mol), it is required to control the feed amountof the halogenated hydrocarbon compound, wherein the amount of Cl to besubstituted is 1 per molecule, to 18 mol or less.

Although the content of fluorine in the antimony halide compound isreduced when the reaction proceeds, the antimony halide compound whosefluorine content was reduced can be regenerated by fluorinating withhydrogen fluoride. When the rate of the reaction of regenerating theantimony halide compound is higher than that of the main reaction (thereaction of fluorinating the halogenated hydrocarbon compound in thepresent invention), the antimony halide compound can be fluorinatedsimultaneously with the main reaction during the main reaction in thereaction field of the main reaction. In the case of the continuousreaction, the halogenated hydrocarbon compound is preferably fed so thatthe fluorination reaction of the antimony halide compound proceedssimultaneously. When the rate of the reaction of regenerating theantimony halide compound is lower than that of the main reaction, thefluorine content of the antimony halide compound is continuously reducedwith proceeding of the main component and the reactivity of the antimonyhalide compound is also lowered. It is also possible to cope with thesituation in such a case by separately fluorinating the antimony halidecompound, the fluorine content of which was reduced.

Examples of the mode for carrying out the present invention include thefollowings.

As the first mode, for example, there is such a mode that apredetermined amount of a halogenated hydrocarbon compound is fed to thereaction field containing a mixture of an antimony halide compound andhydrogen fluoride in a ratio defined in the present invention and thefluorination reaction is conducted. In this case, while only thehalogenated hydrocarbon compound is fed to the reaction field, thefluorination reaction of the present invention can be preferably carriedout as far as the ratio of the antimony halide compound to hydrogenfluoride is within a range defined in the present invention. Therefore,this mode is suited to the case wherein the reaction is conductedbatch-wise.

As the second mode, for example, there is such a mode that apredetermined amount of a halogenated hydrocarbon compound and hydrogenfluoride (and a antimony halide compound, if necessary) are fed to thereaction field containing an antimony halide compound and hydrogenfluoride, thereby to control so that the ratio of the antimony halidecompound to hydrogen halide is maintained within a preferred rangedefined in the present invention. In this case, the ratio of theantimony halide compound and hydrogen halide, which exist in thereaction field, can be maintained at a preferred value by feeding orsupplementing hydrogen fluoride being consumed with proceeding of thefluorination reaction and feeding or supplementing the antimony halidecompound, if necessary. This mode is particularly suited to the systemin which the reaction of regenerating the antimony halide compound asthe catalyst is conducted simultaneously with the main component byfeeding hydrogen fluoride. Therefore, this mode can be applied widely toa middle system between a batch-wise system and a continuous system.

As the third mode, for example, there is such a mode that after apredetermined fluorination reaction according to the first or secondmode is conducted, the fluorination reaction is once stopped andhydrogen fluoride is fed to the reaction field thereby to regenerate theantimony halide compound, and then the fluorination reaction in thefirst or second mode is conducted again. According to this mode, theprocess of the present invention can be carried out without making thereaction apparatus having the fluorination reaction field to becomplicated.

After the fluorination reaction in the first or second mode isconducted, the antimony halide compound, whose fluorine atom content isreduced, is transferred to a separate apparatus for regeneration, wherethe regeneration reaction of a catalyst compound is conducted, while thefluorination reaction in the first or second can also be conducted inthe reaction apparatus having the fluorination reaction field. In thiscase, although the reaction apparatus becomes slightly complicated, theapparatus can be efficiently utilized by minimizing the time duringwhich the fluorination reaction apparatus can not be used in the mainreaction.

Hydrogen chloride produced during the reaction is preferably extractedfrom the reaction vessel. The product can be extracted during thereaction or after the completion of the reaction.

As described above, the reaction of the present invention can beconducted batch-wise or continuously. Even when using any system, thereaction product can be separated and recovered by subjecting theeffluent obtained from the fluorination reaction to a suitable treatmentof distillation, partition, or extraction and separation whilecontacting with an extractant. While the example of using thehalogenated hydrocarbon compound containing only chlorine atoms as theraw material is given in the above description, the process of thepresent invention is not limited the example and can be applied to anycase wherein the halogenated hydrocarbon compound as the raw materialcontains one, two or three kinds selected from the group consisting ofchlorine atom, bromine atom and iodine atom. As a result, afluorine-containing halogenated hydrocarbon compound containing a largeramount of fluorine atoms can be obtained.

As the material of the reaction apparatus, which can be used in thepresent invention, so-called nickel alloys containing Ni as a maincomponent, for example, Ni, Ni—Mo, Ni—Cr, Ni—Cu, Ni—Cr—Mo andNi—Cr—Mo—Fe—Cu alloys are preferred. Preferred examples of these alloysinclude alloys having the following trade names: Monel 400 (JIS NCuP),Monel 500 (JIS NCUATP), Hastelloy B-2 (JIS NM2P), Hastelloy C-22,Hastelloy C-276 (JIS NMCrP), Hastelloy G (JIS NCrFMCu1P), Inconel 600(JIS NCF600), Inconel 625 (JIS NCF625) and Inconel 825 (JIS NCF825).Depending on the reaction temperature, a stainless steel (for example,JIS Symbol SUS 304L or SUS 316L), copper and a copper alloy can also beused.

INDUSTRIAL APPLICABILITY

According to the present invention, by fluorinating, in the reactionfield where an antimony halide compound represented by the generalformula:

SbCl_(p)F_(5−p)  (I)

wherein p is a value within a range from 0 to 2, and hydrogen fluorideand a halogenated hydrocarbon compound as a raw material exist, thehalogenated hydrocarbon compound in a molar ratio of the antimony halidecompound to hydrogen fluoride within a range from 40/60 to 90/10, afluorine-containing halogenated hydrocarbon compound can be preparedwith good selectivity in good yield as shown in Table 1 and,furthermore, the corrosiveness to a metal can be reduced to a low levelas shown in Table 2 to Table 4.

EXAMPLES

Specific examples of the present invention will be describedhereinafter, but the present invention is not limited to embodiments ofthe following examples.

Example 1A

In a 500 ml autoclave equipped with a condenser, 216.7 9 (1.0 mol) ofSbF₅ was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 20 g (1.0 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 43.3 g (0.2 mol) of 1,1,1,3,3-pentachloropropanewas charged in the autoclave over one hour. Therefore, in this example,an antimony halide compound having a composition represented by SbF₅ wasused.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Example 1B

In a 500 ml autoclave equipped with a condenser, 173 g (0.8 mol) of SbF₅was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 24 g (1.2 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 43.3 g (0.2 mol) of 1,1,1,3,3-pentachloropropanewas charged in the autoclave over one hour. Therefore, in this example,an antimony halide compound having a composition represented by SbF₅ wasused.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Example 1C

In a 500 ml autoclave equipped with a condenser, 195 g (0.9 mol) of SbF₅was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 2 g (0.1 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 43.3 g (0.2 mol) of 1,1,1,3,3-pentachloropropanewas charged in the autoclave over one hour. Therefore, in this example,an antimony halide compound having a composition represented by SbF₅ wasused.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Example 2

In a 500 ml autoclave equipped with a condenser, 173.4 g (0.8 mol) ofSbF₅ and 59.8 g (0.2 mol) of SbCl₅ were charged, stirred at 80° C. for30 minutes, and then ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 20 g (1.0 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 43.3 g (0.2 mol) of 1,1,1,3,3-pentachloropropanewas charged in a reaction vessel over one hour. Therefore, in thisexample, an antimony halide compound having a composition represented bySbClF₄ was prepared and used.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Example 3

In a 500 ml autoclave equipped with a condenser, 130.0 g (0.6 mol) ofSbF₅ and 119.6 g (0.4 mol) of SbCl₅ were charged, stirred at 80° C. for30 minutes, and then ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 20 g (1.0 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 43.3 g (0.2 mol) of 1,1,1,3,3-pentachloropropanewas charged in a reaction vessel over one hour. Therefore, in thisexample, an antimony halide compound having a composition represented bySbCl₂F₃ was prepared and used.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Example 4

In a 500 ml autoclave equipped with a condenser, 216.7 g (1.0 mol) ofSbF₅ was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 20 g (1.0 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 20° C. under autogenous pressure. In a reaction vessel, 43.3 g (0.2mol) of 1,1,1,3,3-pentachloropropane was charged over one hour.

The generated gas was collected by a dry ice/acetone trap under reducedpressure (0.05 to 0.001 MPa). The collected organic material wasanalyzed by gas chromatography and the yield was determined. The resultsare shown in Table 1.

Example 5

In a 500 ml autoclave equipped with a condenser, 216.7 g (1.0 mol) ofSbF₅ was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 20 g (1.0 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 33.4 g (0.2 mol) of1,1-dichloro-3,3,3-trifluoropropane was charged in the autoclave overone hour.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Example 6

In a 500 ml autoclave equipped with a condenser, 216.7 g (1.0 mol) ofSbF₅ was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 20 g (1.0 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 26.1 g (0.2 mol) of(E)-1-chloro-3,3,3-trifluoro-1-propene was charged in the autoclave overone hour.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Example 7

In a 500 ml autoclave equipped with a condenser, 216.7 g (1.0 mol) ofSbF₅ was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 20 g (1.0 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 17 g (0.2 mol) of methylene chloride was charged inthe autoclave over one hour.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Example 8

In a 500 ml autoclave equipped with a condenser, 216.7 g (1.0 mol) ofSbF₅ was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 20 g (1.0 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 100° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 33.2 g (0.2 mol) of tetrachloroethylene and 12 g(0.6 mol) of hydrogen fluoride were charged in the autoclave over onehour, followed by continuous stirring for one hour.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Comparative Example 1

In a 500 ml autoclave equipped with a condenser, 108.5 g (0.5 mol) ofSbF₅ was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 90 g (4.5 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 43.3 9 (0.2 mol) of 1,1,1,3,3-pentachloropropanewas charged in the autoclave over one hour.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

Comparative Example 2

In a 500 ml autoclave equipped with a condenser, 21.7 g (0.1 mol) ofSbF₅ was charged and ice-cooled. After the interior of the autoclave wasevacuated to a pressure of about 0.01 MPa and deaerated, 198 g (9.9 mol)of hydrogen fluoride was introduced and the temperature was maintainedat 80° C. under autogenous pressure. The temperature of the condenserwas set to 5° C. and 43.3 g (0.2 mol) of 1,1,1,3,3-pentachloropropanewas charged in the autoclave over one hour.

The generated gas was collected by a dry ice/acetone trap under normalpressure. The collected organic material was analyzed by gaschromatography and the yield was determined. The results are shown inTable 1.

TABLE 1 (first column) Example Example Example Example Example Example1A 1B 1C 2 3 4 SbF₅ (mol) 1.0 0.8 0.9 0.8 0.6 1.0 SbCl₅ (mol) 0 0 0 0.20.4 0 HF (mol) 1.0 1.2 0.1 1.0 1.0 1.0 Molar ratio of (SbF₅ + SbCl₅) to50.0 40.0 90.0 50.0 50.0 50.0 (SbF₅ + SbCl₅ + HF) (mol %) Halogenatedhydrocarbon as raw material (mol) CCl₃CH₂CHCl₂ 0.2 0.2 0.2 0.2 0.2 0.2CF₃CH₂CHCl₂ CF₃CH═CHCl CH₂Cl₂ CCl₂═CCl₂ Reaction temperature (° C.) 8080 80 80 80 20 Yield (mol %) 95 95 94 94 94 97 Composition of product(mol %) CF₃CH₂CHF₂ 100 100 99 99 92 98 CF₃CH₂CHClF 0 0 1 1 5 1CF₃CH₂CHCl₂ 0 0 0 0 3 1 CH₂F₂ CH₂ClF CH₂Cl₂ CF₃CHClF CF₃CHCl₂ CClF₂CHCl₂(second column) Comp. Comp. Example Example Example Example ExampleExample 5 6 7 8 1 2 SbF₅ (mol) 1.0 1.0 1.0 1.0 0.5 0.1 SbCl₅ (mol) 0 0 00 0 0 HF (mol) 1.0 1.0 1.0 1.0 4.5 9.9 Molar ratio of (SbF₅ + SbCl₅) to50.0 50.0 50.0 50.0 10.0 1.0 (SbF₅ + SbCl₅ + HF) (mol %) Halogenatedhydrocarbon (mol) CCl₃CH₂CHCl₂ 0.2 0.2 CF₃CH₂CHCl₂ 0.2 CF₃CH═CHCl 0.2CH₂Cl₂ 0.2 CCl₂═CCl₂ 0.2 Reaction temperature (° C.) 80 80 80 100 80 80Yield (mol %) 97 96 95 98 97 97 Composition of product (mol %)CF₃CH₂CHF₂ 100 100 100 90 CF₃CH₂CHClF 0 0 0 4 CF₃CH₂CHCl₂ 0 0 0 6 CH₂F₂99 CH₂ClF 1 CH₂Cl₂ 0 CF₃CHClF 2 CF₃CHCl₂ 95 CClF₂CHCl₂ 3

Example 9-A1

Three metal pieces of Hastelloy C22 (about 1 cm in width, about 2.5 cmin length and about 0.3 cm in thickness), each size and weight of whichwere previously measured after degreasing and cleaning, were put in a500 ml autoclave equipped with a condenser so that they are not incontact with each other. In the autoclave, a solution prepared bypreviously mixing 651 g (3.0 mol) of SbF₅ with 60 g (3.0 mol) ofhydrogen fluoride was added and the solution was slowly stirred for 100hours while maintaining at a temperature of 80° C. After the autoclavewas cooled with a dry ice/acetone bath, the metal pieces were taken outfrom the autoclave. After the metal pieces were washed with water anddried, each weight was measured. Each corrosion rate (mm/y) of threemetal pieces was calculated by applying the results of a change inweight to the following equation:

Corrosion rate (mm/y)=(87.60×x)/(d×s×t)

where x is a weight loss (mg) due to corrosion, d is a density (g/cm³)of a metal piece, s is a surface area (cm²) of a metal piece, and t is atest time (hr), and then an average thereof was determined and was takenas a corrosion rate of Hastelloy C22. The results are shown in Table 2.

Example 9-A2

Three metal pieces of Hastelloy C22 (about 1 cm in width, about 2.5 cmin length and about 0.3 cm in thickness), each size and weight of whichwere previously measured after degreasing and cleaning, were put in a500 ml autoclave equipped with a condenser so that they are not incontact with each other. In the autoclave, a solution prepared bypreviously mixing 521 g (2.4 mol) of SbF₅ with 72 g (3.6 mol) ofhydrogen fluoride was added and the solution was slowly stirred for 100hours while maintaining at a temperature of 80° C. Thereafter, the sameoperation as in Example 9-A1 was conducted and the corrosion rate wasdetermined. The results are shown in Table 2.

Example 9-B1

Three metal pieces of Hastelloy C276 (about 1 cm in width, about 2.5 cmin length and about 0.3 cm in thickness), each size and weight of whichwere previously measured after degreasing and cleaning, were put in a500 ml autoclave equipped with a condenser so that they are not incontact with each other. In the autoclave, a solution prepared bypreviously mixing 651 g (3.0 mol) of SbF₅ with 60 g (3.0 mol) ofhydrogen fluoride was added and the solution was slowly stirred for 100hours while maintaining at a temperature of 80° C. Thereafter, the sameoperation as in Example 9-A1 was conducted and the corrosion rate wasdetermined. The results are shown in Table 2.

Example 9-B2

Three metal pieces of Hastelloy C276 (about 1 cm in width, about 2.5 cmin length and about 0.3 cm in thickness), each size and weight of whichwere previously measured after degreasing and cleaning, were put in a500 ml autoclave equipped with a condenser so that they are not incontact with each other. In the autoclave, a solution prepared bypreviously mixing 521 g (2.4 mol) of SbF₅ with 72 g (3.6 mol) ofhydrogen fluoride was added and the solution was slowly stirred for 100hours while maintaining at a temperature of 80° C. Thereafter, the sameoperation as in Example 9-A1 was conducted and the corrosion rate wasdetermined. The results are shown in Table 2.

Example 9-C

In the same manner as in Example 9-A, except that Inconel 600 was usedas the material of the metal pieces to be tested, each corrosion rate ofInconel 600 metal pieces was determined. The results are shown in Table2.

Example 9-D

In the same manner as in Example 9-A, except that Monel 400 was used asthe material of the metal pieces to be tested, each corrosion rate ofMonel 400 metal pieces was determined. The results are shown in Table 2.

Example 9-E

In the same manner as in Example 9-A, except that stainless steel 316Lwas used as the material of the metal pieces to be tested, eachcorrosion rate of stainless steel 316L metal pieces was determined. Theresults are shown in Table 2.

Comparative Example 3-A

In the same manner as in Example 9-A, except that a solution containing260.0 g (1.2 mol) of SbF₅ and 56 g (2.8 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 3-B

In the same manner as in Example 9-B, except that a solution containing260.0 g (1.2 mol) of SbF₅ and 56 g (2.8 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 4-A

In the same manner as in Example 9-A, except that a solution containing151.9 g (0.7 mol) of SbF₅ and 126 g (6.3 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 4-B

In the same manner as in Example 9-B, except that a solution containing151.9 g (0.7 mol) of SbF₅ and 126 g (6.3 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 4-C

In the same manner as in Example 9-C, except that a solution containing151.9 g (0.7 mol) of SbF₅ and 126 g (6.3 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 4-D

In the same manner as in Example 9-D, except that a solution containing151.9 g (0.7 mol) of SbF₅ and 126 g (6.3 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 4-E

In the same manner as in Example 9-E, except that a solution containing151.9 g (0.7 mol) of SbF₅ and 126 g (6.3 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 5-A

In the same manner as in Example 9-A, except that a solution containing21.7 g (0.1 mol) of SbF₅ and 198 g (9.9 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 5-B

In the same manner as in Example 9-B, except that a solution containing21.7 g (0.1 mol) of SbF₅ and 198 g (9.9 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 5-C

In the same manner as in Example 9-C, except that a solution containing21.7 g (0.1 mol) of SbF₅ and 198 g (9.9 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 5-D

In the same manner as in Example 9-D, except that a solution containing21.7 g (0.1 mol) of SbF₅ and 198 g (9.9 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

Comparative Example 5-E

In the same manner as in Example 9-E, except that a solution containing21.7 g (0.1 mol) of SbF₅ and 198 g (9.9 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 2.

TABLE 2 SbF₅/SbF₅ + Reaction Corrosion SbF₅ HF HF temperature rate (mol)(mol) (mol %) (° C.) Sample (mm/y) Example 9-A1 3.0 3.0 50 80 HastelloyC22 0.05 Example 9-A2 2.4 3.6 40 80 Hastelloy C22 0.1 Comp. Example 3-A1.2 2.8 30 80 Hastelloy C22 1.0 Comp. Example 4-A 0.7 6.3 10 80Hastelloy C22 4.0 Comp. Example 5-A 0.1 9.9 1 80 Hastelloy C22 2.0Example 9-B1 3.0 3.0 50 80 Hastelloy C276 0.04 Example 9-B2 2.4 3.6 4080 Hastelloy C276 0.08 Comp. Example 3-B 1.2 2.8 30 80 Hastelloy C2760.9 Comp. Example 4-B 0.7 6.3 10 80 Hastelloy C276 4.0 Comp. Example 5-B0.1 9.9 1 80 Hastelloy C276 2.0 Example 9-C 3.0 3.0 50 80 Inconel 6000.1 Comp. Example 4-C 0.7 6.3 10 80 Inconel 600 17 Comp. Example 5-C 0.19.9 1 80 Inconel 600 6.0 Example 9-D 3.0 3.0 50 80 Monel 400 0.1 Comp.Example 4-D 0.7 6.3 10 80 Monel 400 15 Comp. Example 5-D 0.1 9.9 1 80Monel 400 5.0 Example 9-E 3.0 3.0 50 80 Stainless steel 0.8 316L Comp.Example 4-E 0.7 6.3 10 80 Stainless steel 41 316L Comp. Example 5-E 0.19.9 1 80 Stainless steel 20 316L

Example 10-A

The same operation as in Example 9-A was conducted, except that thetemperature maintained in the step of stirring the metal pieces in themixed solution of SbF₅ and hydrogen fluoride for 100 hours was changedto 20° C., the corrosion rate was determined. The results are shown inTable 3.

Example 10-B

The same operation as in Example 9-B was conducted, except that thetemperature maintained in the step of stirring the metal pieces in themixed solution of SbF₅ and hydrogen fluoride for 100 hours was changedto 20° C., the corrosion rate was determined. The results are shown inTable 3.

Comparative Example 6-A

In the same manner as in Example 10-A, except that a solution containing151.9 g (0.7 mol) of SbF₅ and 126 g (6.3 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 3.

Comparative Example 6-B

In the same manner as in Example 10-B, except that a solution containing151.9 g (0.7 mol) of SbF₅ and 126 g (6.3 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 3.

Comparative Example 7-A

In the same manner as in Example 10-A, except that a solution containing21.7 g (0.1 mol) of SbF₅ and 198 g (9.9 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 3.

Comparative Example 7-B

In the same manner as in Example 10-B, except that a solution containing21.7 g (0.1 mol) of SbF₅ and 198 g (9.9 mol) of hydrogen fluoride wasused as the solution to be charged in the autoclave, together with themetal pieces to be tested, the corrosion rate was determined. Theresults are shown in Table 3.

TABLE 3 Reaction SbF₅ HF SbF₅/SbF₅ + HF temperature Corrosion rate (mol)(mol) (mol %) (° C.) Sample (mm/y) Example 10-A 3.0 3.0 50 20 Hastelloy0.00 C22 Comp. Example 0.7 6.3 10 20 Hastelloy 1.0 6-A C22 Comp. Example0.1 9.9 1 20 Hastelloy 0.5 7-A C22 Example 10-B 3.0 3.0 50 20 Hastelloy0.00 C276 Comp. Example 0.7 6.3 10 20 Hastelloy 1.0 6-B C276 Comp.Example 0.1 9.9 1 20 Hastelloy 0.4 7-B C276

Example 11-A

Three metal pieces of Hastelloy C22 (about 1 cm in width, about 2.5 cmin length and about 0.3 cm in thickness), each size and weight of whichwere previously measured after degreasing and cleaning, were put in a500 ml autoclave equipped with a condenser so that they are not incontact with each other. In the autoclave containing the metal pieces, asolution prepared by previously mixing 520 g (2.4 mol) of SbF₅ with179.4 g (0.6 mol) of SbCl₅, stirring at 80° for 30 minutes and adding 60g (3.0 mol) of hydrogen fluoride was charged and the solution was slowlystirred for 100 hours while maintaining at a temperature of 20° C.Thereafter, the same operation as in Example 9-A was conducted and thecorrosion rate was determined. The results are shown in Table 4.

Example 11-B

In the same manner as in Example 11-A, except that Hastelloy C276 wasused as the material of the metal pieces to be tested, each corrosionrate of Hastelloy C276 metal pieces was determined. The results areshown in Table 4.

Comparative Example 8-A

In the same manner as in Example 11-A, except that a solution containing12.1 g (0.08 mol) of SbF₅, 6.0 g (0.02 mol) of SbCl₅ and 198 g (9.9 mol)of hydrogen fluoride was used as the solution to be charged in theautoclave, together with the metal pieces to be tested, the corrosionrate was determined. The results are shown in Table 4.

Comparative Example 8-B

In the same manner as in Example 11-B, except that a solution containing12.1 g (0.08 mol) of SbF₅, 6.0 g (0.02 mol) of SbCl₅ and 198 g (9.9 mol)of hydrogen fluoride was used as the solution to be charged in theautoclave, together with the metal pieces to be tested, the corrosionrate was determined. The results are shown in Table 4.

TABLE 4 SbF₅/SbF₅ + Reaction Corrosion SbF₅ SbCl₅ HF HF temperature rate(mol) (mol) (mol) (mol %) (° C.) Sample (mm/y) Example 11-A 2.4 0.6 3.050 20 Hastelloy 0.00 C22 Comp. Example 8-A 0.08 0.02 9.9 1 20 Hastelloy0.3 C22 Example 11-B 2.4 0.6 3.0 50 20 Hastelloy 0.00 C276 Comp. Example8-B 0.08 0.02 9.9 1 20 Hastelloy 0.4 C276

What is claimed is:
 1. A process for preparing a fluorine-containinghalogenated hydrocarbon compound by fluorinating, in a reaction fieldwhere an antimony halide compound represented by the general formula:SbCl_(p)F_(5−p)  (I) wherein p is a value within a range from 0 to 2,and hydrogen fluoride and a halogenated hydrocarbon compound as a rawmaterial exist, said halogenated hydrocarbon compound in a molar ratioof said antimony halide compound to hydrogen fluoride within a rangefrom 40/60 to 90/10.
 2. The process according to claim 1, wherein saidfluorine-containing halogenated hydrocarbon compound is prepared bybringing a mixture containing 40 to 90 mol % of said antimony halidecompound and 60 to 10 mol % of hydrogen fluoride into contact with saidhalogenated hydrocarbon compound in said reaction field.
 3. The processaccording to claim 1 or 2, wherein said halogenated hydrocarbon compoundas said raw material and hydrogen fluoride are fed to said reactionfield.
 4. The process according to claim 1, wherein a halogenatedhydrocarbon compound represented by the general formula:C_(n)H_(x)Cl_(y)F_(z)  (II) wherein n is any integer of from 1 to 3,when n is 1, x is any integer of from 0 to 2, y is any integer of from 1to 4, z is any integer of from 0 to 2, and x, y and z satisfy therelationship: x+y+z=4, when n is 2, x is any integer of from 0 to 3, yis any integer of from 1 to 6, z is any integer of from 0 t 3, and x, yand z satisfy the relationship: x+y+z=6 or x+y+z=6, and when n is 3, xis any integer of from 0 to 3, y is any integer from 1 to 8, z is anyinteger from 0 to 6, and z, y and z satisfy the relationship x+y+z=8, isused as said raw material to prepare a fluorine-containing halogenatedhydrocarbon compound represented by the general formula:C_(n)H_(x)Cl_(y-a)F_(z+a)  (III)  wherein n is any integer of from 1 to3, when n is 1, x is any integer of from 0 to 2, y is any integer offrom 1 to 4, z is any integer of from 0 to 3, a is any integer of from 1to 4, and x, y, z, and a satisfy the relationships: x+y+z=4 and y≧a,when n is 2, x is any integer of from 0 to 3, y is any integer of from 1to 6, z is any integer of from 0 to 4, a is any integer from 1 to 6, andz, y, z and a satisfy the relationship: x+y+z=4 or x+y+z=6 and therelationship: y≧a, and when n is 3, x is any integer of from 0 to 3, yis any integer of from 1 to 8, z is any integer of from 0 to 7, a is anyinteger of from 1 to 8, and x, y, z and a satisfy the relationship:x+y+z=6 or x+y+z=8 and the relationship: y≧a.
 5. The process accordingto claim 1, wherein said hologenated hydrocarbon compound used as saidraw material is at least one compound selected from the group consistingof CH₂Cl₂ and CH₂ClF, and at least one fluorine-containing halogenatedhydrocarbon compound selected from the group consisting of CH₂ClF andCH₂F₂ is prepared.
 6. The process according to claim 1, wherein saidholgenated hydrocarbon compound used as said raw material is at leastone compound selected from the group consisting of compounds representedby the molecular formulas: C₂Cl₄, C₂HCl₃, C₂HCl₅, C₂HCl₄F, C₂HCl₃F₂,C₂HCl₂F₃, C₂HClF₄, C₂H₂CH₃F, C₂H₂Cl₂F and C₂H₂ClF₃, and one or morefluorine-containing halogenated hydrocarbon compounds represented by themolecular formulas: C₂HCl₄F, C₂HCl₃F₂, C₂HCl₂F₃, C₂HClF₄, C₂HF₅,C₂H₂Cl₃F, C₂H₂ClF₂, C₂H₂ClF₃ and C₂H₂F₄ are prepared.
 7. processaccording to claim 1, wherein said halogenated hydrocarbon compound usedas said raw material is at least one compound selected from the groupconsisting of CCl₃CH₂CHCl₂, CCl₂FCH₂CHCl₂, CCl₃CH₂CHCl₂, CF₃CH₂CHCl₂,CF₃CH₂CHClF, CCl₃CH₂CHClF, CCl₂FCH₂CHClF, CClF₂CH₂CHClF, CCl₃CH₂CHF₂,CCl₂FCH₂CHF₂, CClF₂, CH₂CHF₂ CHCl₂CH═CCl₂, CHCl₂CH═CClF, CHCl₂CH═CF₂,CHClFCH═CCl₂, CHClFCH═CClF, CHClFCH═CF₂, CHF₂CH═CCl₂, CHF₂CH═CClF,CCl₃CH═CHCl, CCl₂FCH═CHCl, CClF₂CH═CHCl, CF₃CH═CHCl, CCl₃CH═CHF,CCl₂FCH═CHF and CClF₂CH═CHF, and at least one fluorine-containinghalogenated hydrocarbon compound selected from the group consisting ofCCl₂FCH₂CHCl₂, CClF₂CH₂CHCl₂, CF₃CH₂CHCl₂, CF₃CH₂CHClF, CCl₃CH₂CHClF,CCl₂FCH₂CHClF, CClF₂CH₂CHClF, CCl₃CH₂CHF₂, CClF₂CH₂CHF₂, CHCl₂CH═CClF,CHCl₂CH═CF₂, CHClFCH═CCl₂, CHClFCH═CClF, CHClFCH═CF₂, CHF₂CH═CCl₂,CHF₂CH═CClF, CCl₂FCH═ChCI, CCIF₂CH═CCl₂, CHF₂CH═CClF, CCl₂FCH═CHCl,CClF₂CH═CHCl, CF₃CH═CHCl, CCl₃CH═CHF, CCl₂FCH═CHF, CClF₂CH═CHF,CF₃CH₂CHF₂, CF₃CH═CHF and CHF₂CH═CF₂ is prepared.